Color photographic light sensitive material

ABSTRACT

THE COLOR DENSITY OF PHOTOGRAPHIC LIGHT-SENSITIVE ELEMENTS IS INCREASED BY INCORPORATING IN AN EMULSION LAYER A POLYMER OF CONSTITUENTS REPRESENTED BY THE FOLLOWING FORMULAE:   -CH2-CH(-COO-R)-, -CH2-CH(-CO-NH2)-, -CH2-CH(-COOH)-,   = X,Y,Z   WHEREIN R REPRESENTS AN ALKYL GROUP PREFERABLY HAVING 1 TO 4 CARBON ATOMS AND X, Y, AND Z ARE NUMBERS SATISGYING THE FOLLOWING CONDITIONS: 40&lt;=X&lt;=90 10&lt;=Y&lt;=60 0&lt;=Z&lt;=40 X+Y+Z=100

United States Patent lfiCC 3,764,327 Patented Oct. 9, 1973 US. C]. 96-55 11 Claims ABSTRACT OF THE DISCLOSURE The color density of photographic light-sensitive elements is increased by incorporating in an emulsion layer a polymer of constituents represented by the following formulae:

wherein R represents an alkyl group preferably having 1 to 4 carbon atoms and x, y, and z are numbers satisfying the following conditions:

BACKGROUND OF THE INVENTION Field of the invention The present invention relates to a color photographic light-sensitive material, and more particularly to an improvement in the color density of reversal color images.

Description of the prior art As multiple layer color photographic light-sensitive material having a blue-sensitive emulsion layer, a greensensitive emulsion layer, and a red-sensitive emulsion layer, there is known the so-called coupler-in-emulsion type materials wherein the photographic emulsion layers each contain a silver halide and a coupler forming a color by reaction with the oxidation product of an aromatic amino photographic developing agent. There is also known the so-called coupler-in-developer type material in which a photographic silver halide emulsion layer substantially free from said couplers is developed with the coupler containing-color developer.

The present invention relates to a novel color photographic material which improved the dye density in color images that were color-developed with color developers containing couplers.

Coupler-in-developer type color photographic lightsensitive materials are ordinarily processed in the following manner after exposure. The element is subjected to a black & white development, subjected to red exposure from the back side of the photographic material, developed with a cyan color developer containing a cyan coupler and an aromatic amino photographic developing agent, subjected to a purple exposure from the photographic emulsion layer side thereof, developed with a yellow color developer containing a yellow coupler and an aromatic amino photographic developing agent, and then developed with a magenta color developer containing a magenta coupler and an aromatic amino photo graphic developing agent.

SUMMARY OF THE INVENTION The present invention relates to a novel color photographic material improving the density of reversal color images in the cyan color development, yellow color development, and magenta color development, and particularly to an improvement in the color density of the magenta color image.

If the densities of reversal color images can be increased a more effective color reproducing system can be made. In such a case the thickness of the emulsion layers can be reduced, which provides such merits that the sharpness of the color images can be improved and the amount of silver halide incorporated in the emulsion layers can be reduced.

According to this invention for improving the density of reversal color images, a gelatino silver halide emulsion layer containing a polymer as described below as a binder is processed by a color developer containing a color coupler.

The polymer discovered by the inventors for the above purposes has the polymer constitutents:

wherein R represents an alkyl group preferably having 1 to 4 carbon atoms and x, y, and z are numbers satisfythe following conditions:

Preferred range 40x90 60x 10y60 20y40 05 S40 10z40 and x+y +z=100.

Among the polymers satisfying the above tractors, preferred polymers have a mean molecular Weight in the range of from about 5,000 to about 500,000, particularly from about 10,000 to about 100,000. Molecular weights outside the above-mentioned range are also operable to the present invention. Examples of such polymer are illustrated below, but the polymers used in this invention are not to be limited to them. The term polymer used hereafter means copolymer" and should not be limited so-called block copolymers.

(mean molecular weight: 100,000).

(mean molecular weight: 20,000).

The polymers used in this invention are not watersoluble but are soluble in alcohols such as methanol, ethanol, and water-alcohol mixtures. The polymer is thus usually added to a photographic emulsion as a solution of an alcohol or a water-alcohol mixture. The term gelatino photographic emulsion according to the invention implies a photographic emulsion may also contain a hydrophilic organic colloid other than gelatin as the binder of silver halide. As the hydrophilic organic colloid other than gelatin, there is gelatin derivatives, and natural or synthetic resin or polymer usually employed in the art of photographic emulsion manufacturing, such as cellulose, polyvinyl alcohol, etc.

The polymers used in this invention may be added to a gelatino photographic emulsion or may replace a part of the gelatin. The polymer may be added in any stage before coating, but is preferably added between postripening and coating. A suitable amount of polymer is in the range of from about 1% by weight to about 90% by Weight of the total amount of gelatin and the polymer in the gelatino silver halide emulsion.

Particularly preferred results can be obtained when the invention is applied to a gelatino silver iodobromide emulsion but the present invention may be applied to various gelatino silver halide emulsions such as silver bromide silver chlorobromide, silver iodochlorobromide and the like.

The silver halide emulsion used in this invention may be sensitized by a compound having labile sulfur, such as sodium thiosulfate or an allylthiourea; by a thiocyanat-e aurite salt; by a reduction sensitizer such as an amino compound or stannous chloride (see The Theory of the Photographic Process, 3rd ed., 113-116 (1966), published by McMillan Company); by a polyalkylene oxide derivative; or by combinations thereof.

To provide a green sensitivity or a red sensitivity to the silver halide emulsion, dyes capable of sensitizing in the wave length region of from 500 millimicrons to 700 millimicrons, can be added thereto such as 1,1'-diethyl- 2,2 cyanine iodide, 3,3 diethyl 9 methylcarbocyanine iodide, etc. (ibid., pp. 199-232).

The silver halide emulsion may contain a stabilizer such as 4-hydroxy 6 methyl 1,3,3a,7 tetraazaindene (ibid., pp. 344-346), a hardening agent such as formaldehyde or mucobromic acid (ibid., pp. 54-60), and a wetting agent such as saponin or sodium alkylbenzenesulfonate. Such materials are well known in the art and are added for their art-recognized function.

Multiple layer type color photographic material having a gelatino silver halide emulsion layer containing the polymer of this invention io processed by an ordinary coupler-in-developer type color photograptic processing. Thus, each of the cyan, magenta, and yellow color developers contains at least one color developing agent and the ditfusible couplers which will be coupled into cyan, magenta, and yellow respectively.

v As the color developingagent, there may be usedthe well-known p-phenylenediamine derivatives such asMA- amino-N,N-diethylaniline, 4. amino-N,N-diethyl-3-methylaniline, 4 amino-3-methyl-N-methyl-N-(fl-methylsulfoneamidoethyl)aniline, 4-amino 3 methyl-N-ethyl-N- (fi-hydroxyethyl) aniline, etc. (ibid., p. 387).

As the ditfusiblecyan coupler used in' this invention, there can be used the well-known phenolic couplers such as 2-chloro-1-naphthol, 2,4 dichloro-l-naphthol, 2-(oacetamido-fl-phenethyl) 1 hydroxynaphthamide, etc. (ibid., p. 387). i v I As the dilfusible magenta coupler, there can be used the well known open chain methylenic couplers such as acylacetonitrile, Z-cyanoethylbenzofuran, and benzylacetonitrile or cyclic methylene couplers such as 1-phenyl-3- (4-chlorobenzamido) 5 pyrazolone, 1 phenyl-3-(3- nitrobenzoylamino) 5 pyrazolone, l-( 2,4,6-trichlorophenyl) -3- (4-nitroanilino -5-pyrazo1one, etc.

As the diffusible yellow couplers there can be used the well-known acylacetoamide open chain methylenic conplers such as 2 acetanilide, 2 aceto-2',4'-dichloroacetanilide, 2-benzoylacetanilide, 2 benz0yl-2-methoxyacetanilide, etc. (ibid., p. 389 and G. H. Brown et al'., Journal of The American Chemical Society, vol. 79, 2919-2927 (1957) The following examples illustrate preferred modes of the invention in great detail.

EXAMPLE 1 A high-speed gelatin silver iodobromide reversal color photographic emulsion (silver iodide content 3.5 mol percent) that had been subjected to a sulfur sensitization and a gold sensitization was melted by heating and applied on to cellulose triacetate film base in an amount of about 15 mg./ cm. (as silver halide). The binder for the silver iodobromide in the emulsion thus coated was gelatin which contained polymer 2 described above in various ratios. The emulsion layer was exposed using an NSG II-type sensitometer and'subjected' to the following proces sings:

The compositions of the processing baths used in the above processings were as shown below.

Pre-hardener: I

Sulfuric acid (cone), cc.

1.7 Borax (10H O), g. 20 Potassium bromide, g. 2.3 Sodium sulfate, g. 200 37% formaldehyde, cc. 10 Sodium bisulfite, g. 1 Water to make 1000 cc.

Negative developer:

N-methyl-p-aminophenol sulfate, g. S Anhydrous sodium sulfite, g 4 79 Hydroquinone, g. 2 Sodium carbonate (monohydrate), g. 40 Potassium bromide, g. 3.5 Potassium thiocyanate, g. 2.0 0.1% potassium iodide, cc. 12.5 Sodium hydroxide, g. 1.0

Water to make 1000 cc.

Magenta color developer:

Sodium sulfite, g. 5.0 "4-amino 3 methyl-N,N-diethylaniline hydro- Water added to make 1000 cc.

The ratio of binder (gelatin 100% by weight) to silver iodobromide in the gelatin silver halide emulsion was S/ 11 by weight. The results obtained are shown in Table 1.

TABLE 1 Amount Ratio of polymer of Ag in gelatin-polymer developed mixture by color developer Weight Magenta, (mg/100 Dmuj Polymer percent Dmax cmfl) Ag As can be understood from the results shown in the above table, when the polymer of this invention was added,

the-value of D /silver increased'by about 20%.

V EXAMPLE 2 The same procedure as in Example 1 was carried out i using polymer 2 in various ratios as the polymer to be mixed with gelatin. The results obtained are shown in the following table.

TAB LE 2 Amount Ratio of polymer of Ag in gelatin-polymer developed mixture by color developer Weight Magenta, (mg/100 Du, I Polymer percent m. crnfl) Ag i From the above results, it' can be seen that the value of D /Ag increased by about 20% with the addition of polymer 2.

EXAMPLE 3 Thesameprocedure as in Example 1 was carried out using polymer 2, polymer 6 and polymer 7 respectively as the polymer to be mixed with gelatin. The results obtained are shown in the following table.

From the above results it can be seen that the ratio of D /Ag increased by about 20% with the addition of the polymers of this invention.

EXAMPLE 4 Using the same processings as in Example 1, a cyan color developing process (27 C., 5 min.) was carried out in place of the magenta color development using the same color photographic film as prepared in Example 1. Moreover, in the same procedure a yellow color development (27 C., 5 min.) was carried out in place of the magenta color development. The results of the both cases are shown in Table 4 and Table 5 respectively.

The compositions of the cyan color developer and the yellow color developer used were as shown below.

Cyan color developer:

Potassium bromide, g. 20 0.1% potassium iodide, cc. 20 Potassium thiocyanate, g. 3.0 Anhydrous sodium sulfite, g. 10 Sodium carbonate (monohydrate), g. 30 Sodium hydroxide, g. 2.0 S-nitrobenzimidazole nitrate, g. 0.5 2,4-dichl0ro-1-naphthol, g. 2.0 4-amino-3methyl-N,N'-diethylaniline hydrochloride, g. 3.0

Water to make 1000 cc.

Yellow color developer:

Sodium sulfite, g. 5.0 N,N'-diethyl-p phenylenediamine hydrochloride, g. s- 1.2 Sodium carbonate (monohydrate), g. 20.0 Potassium bromide, g. 0.3 0.1% potassium iodide, cc 20 2-benzoyl-(4-p toluenesulfonamide) acetanilide, g. 1.0 Sodium hydroxide, g. 4.0

Water to make 1000 cc.

From the above results it can be seen that the values of D /Ag increased considerably in the cyan developed image and yellow developed image by the addition of the polymers of this invention.

What is claimed is:

1. In a color photographic light-sensitive material of the coupler-in-developer type comprising support having thereon at least one of a red-sensitive gelatin silver halide emulsion layer, a green-sensitive gelatino silver halide emulsion layer, or a blue-sensitive gelatino silver halide emulsion layer, the improvement wherein at least one of the gelatino silver halide emulsion layers contains a polymer having the constituents represented by the formulae:

wherein the ratio of said constituents is OR ONE: 0 OH wherein R represents an alkyl group preferably having 1 to 4 carbon atoms and x, y and z are numbers satisfying the following conditions:

2. The color photographic material according to claim 1 wherein the amount of the polymer is from 1 to 90% by weight based on the total weight of gelatin and polymer in the silver halide emulsion.

3. The color photographic material according to claim 1 wherein the silver halide emulsion containing the polymer is a silver iodobromide emulsion.

4. The color photographic material according to claim 1 wherein the polymer has a mean molecular weight of from about 5,000 to about 500,000.

5. The material as set forth in claim 1 wherein the gelatino silver halide emulsion layer containing the polymer is a magenta color forming-emulsion layer.

6. The color photographic material according to claim 1 wherein x, y and z are numbers satisfying the following conditions:

7. The color photographic material according to claim 4 wherein the polymer has a mean molecular weight of from about 10,000 to about 100,000.

8. The color photographic material according to claim 1 wherein the polymer is a member selected from the group consisting of f on -03 CH CH CH C 5 jun r. /'20 a jar LOOK 0003B; ONE: (mean molecular weight: 10,000) and ONHz OOH wherein the ratio of said constituents is wherein R represents an alkyl group preferably having 1 to 4 carbon atoms and x, y, and z are numbers satisfying the following conditions:

' 00065115 O mean molecular weight: 20,000),

- 00cm, onn'l (mean molecular weight: 100,000),

on -on on 425 01; -CH a /;o\. 2 /2o\ 2 L in 0021 1; cum (mean molecular weight: 10,000),

9 r -\w CH-CH CH-CH 1 /4o\ 3 /2o\ 3 /4o OOCH; ONE, noon (mean molecular weight: 70,000), and

\ /o 1'20 jzo COOClHI ooNm. oorr. (mean molecular weight: 20,000).

References Cited UNITED STATES PATENTS 9/1966 Allentoif 961l4 12/ 1967 Firestine 96-114 1/1971 Hughes -Q. 96114 3,597,215 8/1971 7 Abel 96114 3,619,195 11/1971 Van Campen 96-74 NORMAN o. TORCHIN, Primary Examiner A. T. SURO PICO, Assistant Examiner US. Cl. X.R. 

